Water-dispersing coated shaped bodies and their utilization

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Reexamination Certificate

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C428S332000, C428S412000, C428S426000, C428S480000, C428S500000, C428S523000, C428S697000, C428S702000

Reexamination Certificate

active

06565967

ABSTRACT:

The present invention relates to coated mouldings with a water-spreading coating and to the use thereof.
The term “water-spreading” is to be understood to mean the property of a surface for forming a contact angle of below 20 degrees with a drop of water applied on it. A water-spreading coating is accordingly a coating that brings about this property of a surface.
Mouldings with a water-spreading surface have the property that water which gets onto their surface is not concentrated there into drops which are separate from one another but rather that the drops spread out and, when they come into contact, run together to form a closed layer. As a result, an improved reflection of light on the surface that is moistened with water and a better transmission of light in the case of transparent mouldings are achieved. In addition, the dripping of water from the underside of the moulding is rendered difficult. These so-called anti-drop properties which impede the formation of drops are demanded, in particular, for various glazing materials consisting of inorganic glasses (hereinafter called glass for short) or of thermoplastics. In such cases it is desired that condensed water or condensate water deposited thereon does not fall off in the form of drops but rather that it runs off, following the downward gradient of the material, in a closed layer or at least in coherent paths on the lower edge.
Behaviour contrary to that of a water-spreading surface is displayed by the water-repellent surface. On water-repellent surfaces, water which gets onto such a surface is concentrated into drops that are separate from one another.
Numerous attempts to provide water-repellent surfaces of plastics with water-spreading layers are known from the literature. According to DE-A 21 61 645, coatings of this type are produced from a mixed polymer consisting of alkyl esters, hydroxyalkyl esters and quaternary aminoalkyl esters of acrylic or methacrylic acid and methylol ethers of methacrylamide by way of crosslinking agent. They firstly take up water, subject to swelling, and gradually pass over into a water-spreading state. However, as a consequence of the swelling the coating becomes soft and sensitive to mechanical damage.
With a view to improving the mechanical strength of water-spreading coatings, inorganic constituents such as colloidal metal oxides, in particular aluminium oxide, or colloidal silicon dioxide have been worked into the coating compositions (EP-A 7 681 877 or EP-A 7 606 193).
In order to achieve higher mechanical stability, coatings with hydrophilic inorganic constituents in a hydrophilic binding agent have been developed. According to JP-A 76 81 877, polyvinyl-chloride films or polymethyl-methacrylate films are covered with a coating consisting of colloidal aluminium oxide by way of hydrophilising, hard constituent and polyvinyl alcohol and ammonium polyacrylate by way of binding agent. However, in the state swollen with water this coating is also sensitive to mechanical loads.
There have also already been attempts to work wetting-friendly agents into the plastic material itself from which the moulding is produced. For instance, water-spreading coverings for greenhouses and similar damp rooms are produced, according to DE-A 2 017 002, from a plastic that contains surface-active agents such as polyalkylene glycol. The water-spreading effect of this additive is not adequate. The resistance of the plastic to weathering is also impaired.
In JP-A 76 06 193 polymethacrylate sheets with a coating consisting of 95 parts of colloidal silicon dioxide and 5 parts of a dispersion of a hydrophobic acrylic resin are proposed as glazing means. However, the adhesion of this coating is totally unsatisfactory. This is true, above all, with respect to the moist state.
A better adhesion of a water-spreading coating on plastic mouldings is achieved, according to EP-A 51 405, with a covering synthesised from two layers, both layers containing colloidal silicon dioxide, a partially hydrolysed polysiloxane and polyvinyl alcohol by way of binding agent. The ratio of silicon to carbon is greater in the lower layer than in the outer layer.
Generalising, it is possible to note that although a coating having a good water-spreading property can usually be achieved with strongly hydrophilic covering materials, as a rule the coating is too soft in the swollen state. If it is desired to counteract this disadvantage by means of a stronger crosslinking or less hydrophilicity, then the water-spreading effect declines simultaneously with the mechanical sensitivity. Although silicon dioxide and various other oxides of metals or semimetals combine the advantages of great hardness and good wettability by means of water without swelling, they have the disadvantage that they do not adhere at all.
To the extent that use is made of binding agents with a view to anchoring the oxides on the surface of the plastic, the wettability of the oxides and hence the water-spreading effect of the coating declines, and the disadvantages of the binding agents appear: mechanical sensitivity in the case of hydrophilic binding agents, and insufficient spreading of water in the case of hydrophobic binding agents.
In DE-A 34 00 079 it was proposed to bind a water-spreading layer consisting substantially completely of silicon dioxide or other metal oxides of colloidal particle size, which itself has an insufficient adhesive strength on the layer of plastic, onto the water-repellent surface of a plastic moulding in firmly adhering manner by means of an adhesion-promoting layer of an organic polymer having polar groups that is not soluble in water and that is substantially not swellable.
The use of this adhesion-promoting layer or of other so-called primer layers with a view to better connection of the water-spreading layer to the surface of the plastic necessitates an additional process step in the course of coating, as a result of which the production of coated mouldings becomes more complicated and more costly.
All the named coating agents have the disadvantage that they have to be applied from organic solvents.
The object underlying the present invention is to make available mouldings provided with a water-spreading coating, said coating exhibiting, with simultaneous high mechanical strength, excellent adhesive strength without a layer of adhesion promoter.
In accordance with the invention this object is achieved by means of coated mouldings that can be obtained by coating a part of the surface of the moulding or the entire surface of the moulding with a coating agent containing
A) 0.005 to 2 parts by weight of a compound represented by the general formula
 in which
R
1
is a hydrocarbon residue with 1 to 30 C atoms,
R
2
is hydrogen or a hydrocarbon residue with 1 to 6 C atoms,
A is a single bond or a divalent hydrocarbon residue with 1 to 30 C atoms,
B is a single bond or a divalent hydrocarbon residue with 1 to 30 C atoms,
n is 1, 2, 3 or 4 and
M
n+
is a cation with a positive charge n,
B) 1 to 20 parts by weight of a water-insoluble oxide or of several water-insoluble oxides of a metal or semimetal,
C) 80 to 100 parts by weight of a mixture of an acid and water, consisting of more than 90% water,
with the proviso that the pH value of the coating agent is less than 6.
The present invention consequently provides the coated mouldings that have been described. The present invention further provides the use of the coated mouldings according to the invention as glazing material or as a constituent part of automobiles, greenhouses, swimming pools, stadia, railway stations, factory buildings, roof coverings, walls, lamp covers, architectural glazings, light cupolas, visors, spectacles, graphics, advertising hoardings, displays, packagings or of panes for means of locomotion of all types.
The coated mouldings according to the invention exhibit an excellent adhesive strength of the coating with simultaneous high mechanical strength. Layers of adhesion promoters are not required. A further advantage of the mouldings coated in accordance wi

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